This application is a national stage filing under 35 U.S.C. xc2xa7371 of international application no. PCT/IB00/00349, filed on Mar. 27, 2000, which published in the English language.
The present invention relates to new photoactive polymers, and their use as orientation layers for liquid crystals and in the construction of unstructured and structured optical elements and multi-layer systems.
Different electro-optical effects used for liquid crystal displays (LCD) require alignment layers with very high pretilt angles. Vertically aligned nematic (VAN). LCDs for instance require pretilt angles between 85xc2x0 and 90xc2x0, measured from the surface plane. In the case of hybrid aligned nematic (HAN)-LCDs, the pretilt angle at one of the substrates has to be in the above range, whereas the tilt angle at the other substrate is low (typically 0-10xc2x0). Brushed polyimides which are capable of inducing high pretilt angles suffer from the known drawbacks of the brushing technique. In the case of VAN-LCDs especially scratches caused by brushing and insufficient pretilt angle uniformity are well known problems of the brushing technique. On the other hand, stable photoalignable materials for high pretilt angles, which would solve the above problems, are not known so far.
Most of the known electro-optic LCD-modes suffer from residual birefringence of the liquid crystal layer which results in reduced contrast, intrinsic colours and/or restricted viewing angles. Optical retarders are applied to the LCD to compensate for the residual birefringence. Tilted LC-configurations which are formed upon applying a voltage to the LCD are used in most of the commercialised LCDs to adjust grey scale. The very asymmetric viewing angle dependence of such tilted LC-configurations is optimally compensated if the optical axis of the compensating retarder is tilted as well. Liquid crystal polymers (LCP) which were photoaligned by LPP-materials prior to polymerisation are ideally suited to such an application, as the tilt of the optical axis can principally be adjusted to any value between 0xc2x0 and 90xc2x0 by the adjacent alignment layer. A drawback of known alignment materials inducing very high pretilt angles is their high surface tension which causes wetting problems. Consequently, it is not possible to coat a uniform layer of LCP-prepolymers on top of such alignment layers.
EP-A-0 611 786 (F. Hoffinann-La Roche AG) discloses polymers having isomerisation/dimerisation units of the general formula: 
wherein:
Ma, Mb, Mc signify monomer units for homo- or copolymers;
x, y, z indicate mole fractions of the copolymers, whereby in each case 0 less than xxe2x89xa61; 0xe2x89xa6yxe2x89xa61 and 0xe2x89xa6zxe2x89xa61;
Sa, Sb represent spacer units;
Za, Zb represent molecule units which can undergo photochemical isomerisation/dimerisation;
n is from 4-100 000; and
m is 0 or 1.
These linear and cyclic polymers or oligomers have a photoreactive ethene group for use as orientating layers for liquid crystals.
WO-A-96/10049 (F. Hoffinann-La Roche AG) discloses polymers of the general formula: 
wherein:
M1 and M2 signify monomer units for homo- or copolymers; x and yindicate mole fractions of the comonomers, with in each case 0 less than xxe2x89xa61 and 0xe2x89xa6y less than 1 and x+y=1;
p signifies 4 to 30 000;
S1 and S2 signify spacer units;
Q1 signifies a structural unit of the formula:
xe2x80x94Axe2x80x94(Z1xe2x80x94B)zxe2x80x94Z2xe2x80x94xe2x80x83xe2x80x83IIa;
Q2 signifies a structural unit of the formula:
xe2x80x94Axe2x80x94(Z1xe2x80x94B)zxe2x80x94R1xe2x80x94xe2x80x83xe2x80x83IIb;
A and B each independently signify pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or optionally substituted 1,4-phenylene;,
Z1 and Z2 each independently signify a single covalent bond, xe2x80x94CH2xe2x80x94CH2xe2x80x94, xe2x80x94CH2Oxe2x80x94, xe2x80x94OCH2xe2x80x94, xe2x80x94CONRxe2x80x94, xe2x80x94RNCOxe2x80x94, xe2x80x94COOxe2x80x94 or xe2x80x94OOCxe2x80x94;
R signifies hydrogen or lower alkyl;
R1 signifies hydrogen, optionally substituted alkyl or alkoxy with in each case 1 to 12 carbon atoms, cyano, nitro or halogen;
z signifies 0 or 1;
C signifies a photochemically dimerisable coumarin or quinolinone derivative; and
m and n each independently signify 0 or 1.
These linear and cyclic polymers or oligomers of coumarin and quinolinone derivatives have a photoreactive ethene group and may be used as orienting layers for liquid crystals.
EP-A-0 763 552 (Rolic AG) discloses polymer compositions in which repeating units of general formula I are present: 
wherein
M1 signifies a repeating monomer unit from the group; acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate; optionally N-lower alkyl substituted acrylamide, methacrylamide, 2-chloroacrylamide and 2-phenylacrylamide; vinyl ether, vinyl ester, styrene derivative, siloxane;
S1 signifies spacer units such as, for example, a single covalent bond, a straight-chain or branched alkylene grouping represented hereinafter by xe2x80x94(CH2)rxe2x80x94, as well as xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94 or xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94NR3xe2x80x94, which is optionally mono- or multiply-substituted with fluorine, chlorine or cyano and in which r and s are each a whole number of 1 to 20, with the proviso that r+sxe2x89xa620, and R2 and R3 each independently signify hydrogen or lower alkyl;
ring A signifies phenylene which is unsubstituted or optionally substituted with fluorine, chlorine, cyano, alkyl or alkoxy, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, cyclohexane-1,4-diyl, piperidine-1,4-diyl, piperazine-1,4-diyl;
ring B signifies phenylene which is unsubstituted or optionally substituted with fluorine, chlorine, cyano, alkyl or alkoxy, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,4- or 2,6-naphthylene, 1,3-dioxane-2,5-diyl, cyclohexane-1,4-diyl;
Y1, Y2 each independently signify a single covalent bond, xe2x80x94(CH2)txe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94OCxe2x80x94, xe2x80x94NR4xe2x80x94, xe2x80x94COxe2x80x94NR4xe2x80x94, xe2x80x94R4Nxe2x80x94COxe2x80x94, xe2x80x94(CH2)uxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CB2)uxe2x80x94, xe2x80x94(CH2)uxe2x80x94NR4xe2x80x94 or xe2x80x94NR4xe2x80x94(CH2)uxe2x80x94, in which
R4 signifies hydrogen or lower alkyl;
t signifies a whole number of 1 to 4;
u signifies a whole number of 1 to 3;
m, n each independently signify 0 or 1;
ring C signifies phenylene which is unsubstituted or optionally substituted with fluorine, chlorine, cyano, alkyl or alkoxy, or pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, 1,4- or 2,6-naphthylene;
Z signifies xe2x80x94Oxe2x80x94 or xe2x80x94NR5xe2x80x94, in which R5 signifies hydrogen or lower alkyl, or a second group of formula D, in which
D signifies a straight-chain or branched alkylene group with 1 to 20 carbon atoms which is optionally substituted with fluorine or chlorine, a cycloalkyl residue with 3 to 8 ring atoms which is optionally substituted with fluorine, chlorine alkyl or alkoxy.
These cross-linkable, photoactive polymer materials with 3-arylacrylic acid esters and amides may be used as orienting layers for liquid crystals and for the production of non-structured and structured optical elements and multi-layer systems.
EP-A-0860455 (Rolic AG) discloses polymers of the general formula I: 
wherein:
M1, M1xe2x80x2 denote a recurring monomer unit form the group: acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate; optionally by lower alkyl N-substituted acrylamide, methacrylamide, 2-chloroacrylamide and 2-phenylacrylamide; vinyl ethers, vinyl esters, styrene derivatives, siloxanes;
M2 denotes a recurring monomer unit from the group: acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate, optionally by lower alkyl N-substituted acrylamide, methacrylamide, 2-chloroacrylamide and 2-phenylacrylamide; vinyl ether, vinyl ester; straight-chain or branched alkyl esters of acrylic or methacrylic acid, allyl esters of acrylic or methacrylic acid, alkyl vinyl ethers or ester, phenoxyalkyl acrylates or phenoxyalkyl methacrylates or hydroxyalkyl acrylates or hydroxyalkyl methacrylates, phenylalkyl acrylates or phenylalkyl methacrylates, in which the alkyl groups have 1 to 20, preferably 5 to 20, but in particular 5 to 18 carbon atoms; acrylonitrile, methacrylonitrile, styrene, 4-methylstyrene or siloxanes;
w, w1, w2 are molar fractions of the comonomers with 0 less than wxe2x89xa61.0xe2x89xa6w1 less than 1 and 0xe2x89xa6w2xe2x89xa60.5;
S1, S1xe2x80x2, independently of one another a spacer unit, such as an optionally monosubstituted or polysubstituted by fluorine, chlorine or cyano straight-chain or branched alkylene group xe2x80x94(CH2)rxe2x80x94, or a chain of formula xe2x80x94(CH2)rxe2x80x94Lxe2x80x94(CH2)sxe2x80x94, in which L denotes a single bond or a linkng functional group such as xe2x80x94Oxe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94OOCxe2x80x94, xe2x80x94NRxe2x80x94, xe2x80x94NR1xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR1xe2x80x94, xe2x80x94NR1xe2x80x94COOxe2x80x94, xe2x80x94OCOxe2x80x94NR1xe2x80x94, xe2x80x94NR1xe2x80x94COxe2x80x94NR1xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94; in which R1 denotes hydrogen or lower alkyl and r and s each represent an integer from 1 to 20, with the proviso that r+sxe2x89xa624;
D, Dxe2x80x2 independently of one another xe2x80x94Oxe2x80x94 or NR2xe2x80x94 in which R2 denotes hydrogen or lower alkyl;
X, Xxe2x80x2, Y, Yxe2x80x2 independently of one another denote hydrogen, fluorine, chlorine, cyano, alkyl with 1 to 12 carbon atoms which is optionally substituted with fluorine and in which optionally one CH2 group or a plurality of non-neighbouring CH2 groups may be replaced by O, xe2x80x94COOxe2x80x94, xe2x80x94OOCxe2x80x94, and/or xe2x80x94CHxe2x95x90CHxe2x80x94;
A, Axe2x80x2 independently of one another denote phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, cyclohexane-1,4-diyl, piperidine-1,4-diyl, piperazine-1,4-diyl which is unsubstituted or optionally substituted with fluorine, chlorine, cyano, alkyl, alkoxy or fluoroalkoxy;
B, Bxe2x80x2 independently of one another denote phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,4- or 2,6-naphthylene, 1,3-dioxane-2,5-diyl, cyclohexane-1,4-diyl which is unsubstituted or optionally substituted with fluorine, chlorine, cyano, alkyl, alkoxy or fluoroalkoxy;
C, Cxe2x80x2 independently of one another denote phenylene, or pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, 1,4- or 2,6-naphthylene which is unsubstituted or optionally substituted with fluorine, chlorine, cyano, alkyl, alkoxy or fluoroalkoxy;
K, Kxe2x80x2 independently of one another denote hydrogen, fluorine, chlorine, cyano, nitro or a straight-chain or branched alkyl-, alkoxy-alkyl-COOxe2x80x94, alkyl-COxe2x80x94NR3 or alkyl-OCO-group with 1 to 20 carbon atoms optionally substituted with fluorine, chlorine, cyano or nitro in which optionally a CH2 group or a plurality of non-neighbouring CH2 groups may be replaced by xe2x80x94Oxe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94 or xe2x80x94Cxe2x89xa1Cxe2x80x94 and in which R3 hydrogen or lower alkyl;
with the proviso that at least one of the rings A, B, C and/or at least one of the rings Axe2x80x2, Bxe2x80x2, Cxe2x80x2 represents a phenylene group, which is substituted with at least one alkoxy group or fluoroalkoxy group, in which, if K denotes alkoxy or fluoroalkoxy, at least one of the rings A, B, C and/or at least one of the rings Axe2x80x2, Bxe2x80x2, Cxe2x80x2 represents a phenylene group, which is substituted with at least one further alkoxy group or fluoroalkoxy group;
Z, Zxe2x80x2, Zxe2x80x2, Z1xe2x80x2 independently of one another denote a single covalent bond, xe2x80x94(CH2)txe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94OCxe2x80x94, xe2x80x94NR4xe2x80x94, xe2x80x94COxe2x80x94NR4xe2x80x94, xe2x80x94R4Nxe2x80x94COxe2x80x94, xe2x80x94(CH2)uxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)uxe2x80x94, xe2x80x94(CH2)uxe2x80x94NR4xe2x80x94 or xe2x80x94NR4xe2x80x94(CH2)uxe2x80x94;
in which R4 denotes hydrogen or lower alkyl,
t denotes an integer from 1 to 4;
u denotes an integer from 1 to 3; and
p, pxe2x80x2, n, nxe2x80x2 independently of one another denotes 0 or 1.
These crosslinkable photoactive polymers may be used as orientation layers for liquid crystals and for the production: of unstructured or structured optical elements and mulitilayer systems.
The present invention provides optically active or inactive photoactive polymers of the general formula I: 
in which:
P is a photoactive group which can photoisomerise and/or photodimerise;
B represents an aromatic or alicyclic group which is unsubstituted or substituted by fluorine, chlorine or cyano, or by a cyclic, straight-chain or branched alkyl residue which is unsubstituted, mono-substituted by cyano or halogeno, or poly-substituted by halogeno, having 1 to 18 carbon atoms and wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94Si(CH3)2xe2x80x94, NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94Oxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other, and wherein R2 represents a hydrogen atom or lower alkyl, or B further represents a nitrogen atom or xe2x80x94CR2xe2x80x94;
A, C, D each independently of the other represents an aromatic or alicyclic group which is unsubstituted or substituted by fluorine, chlorine, cyano, or by a cyclic, straight-chain or branched alkyl residue which is unsubstituted, mono-substituted by cyano or halogeno, or poly-substituted by halogeno, having 1 to 18 carbon atoms and wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94Si(CH3)2xe2x80x94, xe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94Oxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other, and wherein R2 represents a hydrogen atom or lower alkyl;
M represents a repeating monomer unit in a homo- or copolymer;
S1, S2, S3, S4, S5 represent a single covalent bond or a spacer unit, such as a straight-chain or branched alkylene residue which is unsubstituted, mono-substituted by cyano or halogeno, or poly-substituted by halogeno, having 1 to 24 carbon atoms, wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94Si(CH3)2xe2x80x94, xe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94Oxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other, and wherein R2 represents a hydrogen atom or lower alkyl;
n1, n2 are each independently 0, 1 or 2 with the proviso that n1+n2xe2x89xa62
R1 is a hydrogen atom, or a straight-chain or branched alkyl residue which is unsubstituted, mono-substituted by cyano or halogeno, or poly-substituted by halogeno, having 1 to 18 carbon atoms, wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94CO, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94Si(CH3)2xe2x80x94, xe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1xe2x80x94Cxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94C), with the proviso that oxygen atoms are not directly attached to each other, and wherein R2 represents a hydrogen atom or lower alkyl.
The invention also provides the use of the polymers of the general formula I as orientation layers for liquid crystals and in the construction of unstructured and structured optical elements and multi-layer systems.
The new photoreactive materials show excellent alignment and induce very high pretilt angles in the liquid crystal layer in LCDs.
Surprisingly these materials can easily be coated with LCP-prepolymers without wetting problems. For example, in a liquid crystal cell the pretilt angle of the optical axis in an LCP-layer is very high. Tilt domains which are sometimes observed in tilted LCP-layers do not show up.
Preferred photoactive groups P are groups which undergo a photocyclisation and have the general formula II and III: 
wherein the broken line indicates the point of linkage to S1 and wherein:
E represents phenylene which is unsubstituted or substituted by fluorine, chlorine or cyano, or by a cyclic, straight-chain or branched alkyl residue which is unsubstituted, mono-substituted by cyano or halogeno, or poly-substituted by halogeno, having 1 to 18 carbon atoms and wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94Si(CH3)2xe2x80x94, xe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94CH=CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94Oxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other, and wherein R2 represents a hydrogen atom or lower alkyl, or E further represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, or 1,4- or 2,6-naphthylene;
F represents xe2x80x94OR4, xe2x80x94NR5R6, or an oxygen atom linked to ring E in the ortho position to form a coumarin unit wherein R4, R5 and R6 are a hydrogen atom or a cyclic, straight-chain or branched alkyl residue which is unsubstituted, mono-substituted by halogeno, or poly-substituted by halogeno, having 1 to 18 carbon atoms and wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other, or R5 and R6 are linked together to form an alicyclic ring with 5 to 8 atoms;
X, Y each independently of the other represents hydrogen, fluorine, chlorine, cyano, alkyl optionally substituted by fluorine having from 1 to 12 carbon atoms in which optionally one or more non-adjacent CH2 groups are replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94 and/or xe2x80x94CHxe2x95x90CHxe2x80x94;
R3 is a hydrogen atom, or a straight-chain or branched alkyl residue which is unsubstituted, mono-substituted by cyano or halogeno, or poly-substituted by halogeno, having 1 to 18 carbon atoms, wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94Si(CH3)2xe2x80x94, xe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94Oxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other, and wherein R2 represents a hydrogen atom or lower alkyl.
Special preferred photoactive groups P have the general formula IV and V: 
wherein the broken line indicates the point of linkage to S1 and wherein R3 has the meaning given under formula II and III;
F represents xe2x80x94OR4 or xe2x80x94NR5R6, wherein R4 and R5 are a cyclic, straight-chain or branched alkyl residue which unsubstituted, mono-substituted by halogeno, or poly-substituted by halogeno, having 1 to 18 carbon atoms and wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94 or xe2x80x94CHxe2x95x90CHxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other, and wherein R6 is a hydrogen atom or a cyclic, straight-chain or branched alkyl residue which is unsubstituted, mono-substituted by halogeno, or poly-substituted by halogeno, having 1 to 18 carbon atoms and wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94 or xe2x80x94CHxe2x95x90CHxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other, or R5 and R6 link together to form an alicyclic zing with 5 to 8 atoms; and
E represents phenylene which is unsubstituted or substituted by a cyclic, straight-chain or branched alkyl residue which is unsubstituted, mono-substituted by halogeno, or poly-substituted by halogeno, having 1 to 12 carbon atoms and wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94CO, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other, or E further represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, 1,4- or 2,6-naphthylene.
Especially preferred photoactive P groups have the general formula IV wherein:
E represents phenylene which is unsubstituted or substituted by a straight-chain or branched alkyl residue which is unsubstituted or mono- or polysubstituted by fluorine, having 1 to 6 carbon atoms and wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94CO, xe2x80x94CHxe2x95x90CHxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other, or E further represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-furanylene, 1,4- or 2,6-naphthylene;
F represents xe2x80x94OR4 or xe2x80x94NHR5, wherein R4 and R5 are a cyclic, straight-chain or branched alkyl residue which is unsubstituted or mono- or polysubstituted by fluorine, having 1 to 18 carbon atoms and wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other.
The preferred polymers of formula I can be further divided into:
a) polymers of formula I in which B represents a aromatic or alicyclic group and where n1+n2=1;
b) polymers of formula I in which B represents a aromatic or alicyclic group and where n1+n2=0;
c) polymers of formula I in which B represents a group xe2x80x94CR2xe2x80x94 and where 0 less than n1+n2xe2x89xa62; and
d) optically inactive polymers of formula I.
Preferred groups B are aromatic which are unsubstituted or substituted by fluorine, chlorine or cyano, or by a cyclic, straight-chain or branched alkyl residue which is unsubstituted, mono-substituted by cyano or halogeno, or poly-substituted by halogeno, having 1 to 18 carbon atoms and wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other, or B further represents xe2x80x94CR2xe2x80x94, wherein R2 represents hydrogen atom or lower alkyl.
Especially preferred groups B are 1,2,5-benzenetriyl and 1,3,5-benzenetriyl groups which are unsubstituted or substituted by fluorine and where the spacer group S5 is in position 1.
Preferred groups A, C and D are phenylene which is unsubstituted or substituted by fluorine, chlorine, cyano, or by a cyclic, straight-chain or branched alkyl residue which is unsubstituted, mono-substituted by cyano or halogeno, or poly-substituted by halogeno, having 1 to 12 carbon atoms, wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94 or xe2x80x94Oxe2x80x94COxe2x80x94Oxe2x80x94 with the proviso that oxygen atoms are not directly attached to each other, or A, C and D further represents cyclohexane-1,4-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,4- or 2,6-naphthylene.
Especially preferred groups A, C and D are phenylene, which is unsubstituted or substituted by fluorine, straight-chain or branched alkyl residue which is unsubstituted or mono- or polysubstituted by fluorine, having 1 to 8 carbon atoms, wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94 or xe2x80x94CHxe2x95x90CHxe2x80x94 with the proviso that oxygen atoms are not directly attached to each other, or A, C and D further represents cyclohexane-1,4-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 2,6-naphthylene.
Preferred xe2x80x9cspacer unitsxe2x80x9d S1, S2, S3, S4 and S5 in the context of the present invention represent a single covalent bond or a spacer unit, such as a straight-chain or branched alkylene grouping represented by (CH2)rxe2x80x94, optionally mono- or poly-substituted by fluorine, chlorine or cyano, or a chain of the formula xe2x80x94L1xe2x80x94(CH2)rxe2x80x94L2xe2x80x94 or xe2x80x94L1xe2x80x94(CH2)rxe2x80x94L2xe2x80x94(CH2)sxe2x80x94L3xe2x80x94, wherein L1, L2 and L3 each independently of the others represent a single bond or linking functional groups such as xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94Si(CH3)2xe2x80x94, wherein R2 represents hydrogen atom or lower alkyl and r and s are each an integer from 1 to 20, with the proviso that r+sxe2x89xa624 and with the proviso that in the case where the repeating monomer unit M is linked to S5 via a nitrogen atom or a oxygen atom which is by definition part of M, as for example in acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate, optionally N-lower alkyl substituted acrylamide, methacrylamide, 2-chloroacrylamide, 2-phenylacrylamide; or a vinyl ether, vinyl ester, maleic acid derivative or fumaric acid derivative; L1 signifies a single bond.
Especially preferred xe2x80x9cspacer unitsxe2x80x9d S1, S2, S3, S4 and S5 in the context of the present invention are a straight-chain or branched alkylene grouping, represented by xe2x80x94(CH2)rxe2x80x94, and also xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, wherein r and s are each an integer from 1 to 20, but especially from 2 to 12, with the proviso that r+sxe2x89xa621, especially xe2x89xa615, and wherein R2 represents hydrogen or lower alkyl.
Most preferred xe2x80x9cspacer unitsxe2x80x9d S1, S2, S3, S4 and S5 are a straight-chain alkylene grouping represented by xe2x80x94(CH2)rxe2x80x94, and also xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94NHxe2x80x94, xe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94NHxe2x80x94(CH2)rxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94NHxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94NHxe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94NHxe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, wherein r and s are each an integer from 2 to 12 and the sum of r+sxe2x89xa615.
Examples of preferred xe2x80x9cspacer unitsxe2x80x9d S1, S2, S3, S4 and S5 are 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 3-methyl-1,4-butylene, 3-propyleneoxy, 3-propyleneoxycarbonyl, 2-ethylenecarbonyloxy, 4-butyleneoxy, 4-butyleneoxycarbonyl, 3-propylenecarbonyloxy, 5-pentyleneoxy, 5-pentyleneoxycarbonyl, 4-butylenecarbonyloxy, 6-hexyleneoxy, 6-hexyleneoxycarbonyl, 5-pentylenecarbonyloxy, 7-heptyleneoxy, 7-heptyleneoxycarbonyl, 6-hexylenecarbonyloxy, 8-octyleneoxy, 8-octyleneoxycarbonyl, 7-heptylenecarbonyloxy, 9-nonyleneoxy, 9-nonyleneoxycarbonyl, 8-octylenecarbonyloxy, 10-decyleneoxy, 10-decyleneoxycarbonyl, 9-nonylenecarbonyloxy, 11-undecyleneoxy, 11-undecyleneoxycarbonyl, 10-decylenecarbonyloxy, 12-dodecyleneoxy, 12-dodecyleneoxycarbonyl, 11-undecylenecarbonyloxy, 3-propyleneiminocarbonyl, 4-butyleneiminocarbonyl, 5-pentyleneiminocarbonyl, 6-hexyleneiminocarbonyl, 7-heptyleneiminocarbonyl, 8-octyleneiminocarbonyl, 9-nonyleneiminocarbonyl, 10-decyleneiminocarbonyl, 11-undecyleneiminocarbonyl, 12-dodecyleneiminocarbonyl, 2-ethylenecarbonylimino, 3-propylenecarbonylimino, 4-butylenecarbonylimino, 5-pentylenecarbonylimino, 6-hexylenecarbonylimino, 7-heptylenecarbonylimino, 8-octylenecarbonylimino, 9-nonylenecarbonylimino, 10-decylenecarbonylimino, 11-undecylenecarbonylimino, 6-(3-propyleneiminocarbonyloxy)hexylene, 6-(3-propyleneoxy)hexylene, 6-(3-propyleneoxy)hexyleneoxy, 6-(3-propyleneiminocarbonyloxy)hexyleneoxy, 6-(3-propyleneiminocarbonyl)hexyl, 6-(3-propyleneiminocarbonyl)hexyloxy, 1,2-ethylenedioxy, 1,3-propylenedioxy, 1,4-butylenedioxy, 1,5-pentylenedioxy, 1,6-hexylenedioxy, 1,7-heptylenedioxy, 1,8-octylenedioxy, 1,9-nonylenedioxy, 1,10-decylenedioxy, 1,11-undecylenedioxy, 1,12-dodecylenedioxy and the like.
Preferred groups R1 are a hydrogen atom, or a straight-chain or branched alkyl residue which is unsubstituted or halogeno or polyhalogeno-substituted, having 1 to 12 carbon atoms, wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94 or xe2x80x94Cxe2x89xa1Cxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other.
Especially preferred groups R1 are straight-chain or branched alkyl residue, having 1 to 8 carbon atoms, wherein one or more CH2 groups are each independently replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94 or xe2x80x94Oxe2x80x94COxe2x80x94 or xe2x80x94CHxe2x95x90CHxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other. For example, methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, allyl, but-3-en-1-yl, pent-4-en-1-yl, hex-5-en-1-yl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 3-methylpentyloxy, but-3-enyloxy, pent-4-enyloxy and the like.
Preferred repeating monomer units M are acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate, optionally N-lower alkyl substituted acrylamide, methacrylamide, 2-chloroacrylamide, 2-phenylacrylamide, vinyl ether, vinyl ester, styrene derivatives, siloxanes, imides, amic acids and their esters, amidimides, maleic acid derivatives, fumaric acid derivatives.
Especially preferred repeating monomer unit M are acrylate, methacrylate, optionally N-lower-alkyl-substituted acrylamide, methacrylamide, vinyl ether, vinyl ester, styrene derivatives, imides, amic acids and there esters, amidimides.
Most preferred repeating monomer units M are acrylate, methacrylate, styrene derivatives, imides, amic acids and their esters, and amidimides.
Preferred imide units M from which the main chains of the side-chain polymers according to the invention are generally synthesised are groups of the general formulae III, V and VII and/or the analogous amic acid groups and amic acid ester groups of the general formulae IV, VI and VIII: 
in which the broken line symbolises the linkage to S5 and wherein:
T1 represents the tetravalent organic radical of a tetracarboxylic acid dianhydride after formal removal of the two xe2x80x94COxe2x80x94Oxe2x80x94COxe2x80x94 groups, the four valencies of which are distributed between four different carbon atoms of the radical;
T2, T3 each independently of the other represents an aromatic or alicyclic trivalent group, the three valencies of which are distributed between three different carbon atoms of the group, the group being unsubstituted or substituted by fluorine, chlorine, cyano, by a cyclic, straight-chain or branched alkyl residue which is unsubstituted, mono-substituted by halogeno, or poly-substituted by halogeno, having 1 to 18 carbon atoms and wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other;
S6, S7, S8, S9, S10 represent a single covalent bond or a spacer unit, such a straight-chain or branched alkylene residue which is unsubstituted, mono-substituted by cyano or halogeno, or poly-substituted by halogeno, having 1 to 24 carbon atoms, wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94Si(CH3)2xe2x80x94, xe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94Oxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other, and wherein R2 represents hydrogen atom or lower alkyl;
J represents an aromatic or alicyclic divalent, trivalent or tetravalent group, the valencies of which are distributed between different atoms of the group, which is unsubstituted or substituted by fluorine, chlorine, cyano, by a cyclic, straight-chain or branched alkyl residue which is unsubstituted or mono cyano, or halogeno or polyhalogeno-substituted, having 1 to 18 carbon atoms and wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, with the proviso that oxygen atoms are not directly attached to each other, or J further represents a nitrogen atom or xe2x80x94CR2xe2x80x94 and wherein R2 represents a hydrogen atom or lower alkyl;
K represents the radical of an aliphatic, alicyclic or aromatic diamine after formal removal of the two amino groups; and
G represents hydrogen atom or a monovalent organic group, derived from an alcohol after formal removal of the hydroxy group.
The tetracarboxylic acid dianhydride on which the tetravalent organic radical T1 is based may be aliphatic, alicyclic or aromatic.
Preferred examples of aliphatic or alicyclic tetracarboxylic acid anhydrides are:
butanetetracarboxylic acid dianhydride;
ethylenemaleic acid dianhydride;
1,2,3,4-cyclobutanetetracarboxylic acid dianhydride;
1,2,3,4-cyclopentanetetracarboxylic acid dianhydride;
2,3,5-tricarboxycyclopentylacetic acid dianhydride;
3,5,6-tricarboxynorbornylacetic acid dianhydride;
2,3,4,5-tetrahydrofurantetracarboxylic acid dianhydride;
4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride;
5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride;
bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride;
bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid dianhydride; and
1,8-dimethylbicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride.
Examples of preferred aromatic tetracarboxylic acid dianhydrides are:
pyromellitic acid dianhydride;
3,3xe2x80x2,4,4xe2x80x2-benzophenonetetracarboxylic acid dianhydride;
4,4xe2x80x2-oxydiphthalic acid dianhydride;
3,3xe2x80x2,4,4xe2x80x2-diphenylsulfonetetracarboxylic acid dianhydride;
1,4,5,8-naphthalenetetracarboxylic acid dianhydride;
2,3,6,7-naphthalenetetracarboxylic acid dianhydride;
3,3xe2x80x2,4,4xe2x80x2-dimethyldiphenylsilanetetracarboxylic acid dianhydride;
3,3xe2x80x2,4,4xe2x80x2-tetraphenylsilanetetracarboxylic acid dianhydride;
1,2,3,4-furantetracarboxylic acid dianhydride;
4,4xe2x80x2-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride;
4,4xe2x80x2-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride;
4,4xe2x80x2-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride;
3,3xe2x80x2,4,4xe2x80x2-biphenyltetracarboxylic acid dianhydride;
ethylene glycol bis(trimellitic acid)dianhydride;
4,4xe2x80x2-(1,4-phenylene)bis(phthalic acid)dianhydride;
4,4xe2x80x2-(1,3-phenylene)bis(phthalic acid)dianhydride;
4,4xe2x80x2-(hexafluoroisopropylidene)diphthalic acid dianhydride;
4,4xe2x80x2-oxydi(1,4-phenylene)bis(phthalic acid)dianhydride; and
4,4xe2x80x2-methylenedi(1,4-phenylene)bis(phthalic acid)dianhydride.
Especially preferred are:
1,2,3,4-cyclobutanetetracarboxylic acid dianhydride;
1,2,3,4-cyclopentanetetracarboxylic acid dianhydride;
2,3,5-tricarboxycyclopentylacetic acid dianhydride;
5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride;
4-(2,5-dioxotetrabydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride;
4,4xe2x80x2-(hexafluoroisopropylidene)diphthalic acid dianhydride; and
bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride.
The groups T2 and T3 can be derived from aliphatic, alicyclic or aromatic dicarboxylic acid anhydrides.
Preferred groups T2 and T3 are trivalent aromatic or carbocyclic groups, the three valencies of which are so distributed between three different carbon atoms that two of those valencies are located at adjacent carbon atoms.
Especially preferred groups T2 and T3 are trivalent benzene derivatives, the three valencies of which are so distributed between three different carbon atoms that two of those valencies are in the ortho position relative to one another.
Preferred xe2x80x9cspacer unitsxe2x80x9d S6 in the context of the present invention are a straight-chain or branched alkylene grouping, represented by xe2x80x94(CH2)rxe2x80x94, and also xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94COxe2x80x94, wherein r and s are each an integer from 1 to 20, but especially from 2 to 12, with the proviso that r+sxe2x89xa621, especially xe2x89xa615, and wherein R2 represents hydrogen or lower alkyl.
Examples of preferred xe2x80x9cspacer unitsxe2x80x9d S6 are 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 3-methyl-1,4-butylene, 3-propyleneoxy, 3-propyleneoxycarbonyl, 2-ethylenecarbonyloxy, 4-butyleneoxy, 4-butyleneoxycarbonyl, 3-propylenecarbonyloxy, 5-pentyleneoxy, 5-pentyleneoxycarbonyl, 4-butylenecarbonyloxy, 6-hexyleneoxy, 6-hexyleneoxycarbonyl, 5-pentylenecarbonyloxy, 7-heptyleneoxy, 7-heptyleneoxycarbonyl, 6-hexylenecarbonyloxy, 8-octyleneoxy, 8-octyleneoxycarbonyl, 7-heptylenecarbonyloxy, 9-nonyleneoxy, 9-nonyleneoxycarbonyl, 8-octylenecarbonyloxy, 10-decyleneoxy, 10-decyleneoxycarbonyl, 9-nonylenecarbonyloxy, 11-undecyleneoxy, 11-undecyleneoxycarbonyl, 10-decylenecarbonyloxy, 12-dodecyleneoxy, 12-dodecyleneoxycarbonyl, 11-undecylenecarbonyloxy, 3-propyleneiminocarbonyl, 4-butyleneiminocarbonyl, 5-pentyleneiminocarbonyl, 6-hexyleneiminocarbonyl, 7-heptyleneiminocarbonyl, 8-octyleneiminocarbonyl, 9-nonyleneiminocarbonyl, 10-decyleneiminocarbonyl, 11-undecyleneiminocarbonyl, 12-dodecyleneiminocarbonyl, 2-ethylenecarbonylimino, 3-propylenecarbonylimino, 4-butylenecarbonylimino, 5-pentylenecarbonylimino, 6-hexylenecarbonylimino, 7-heptylenecarbonylimino, 8-octylenecarbonylimino, 9-nonylenecarbonylimino, 10-decylenecarbonylimino, 11-undecylenecarbonylimino, 6-(3-propyleneiminocarbonyloxy)hexylene, 6-(3-propyleneoxy)hexylene, 6-(3-propyleneoxy)hexyleneoxy, 6-(3-propyleneiminocarbonyloxy)hexyleneoxy, 6-(3-propyleneiminocarbonyl)hexylene, 6-(3-propyleneiminocarbonyl)hexyleneoxy and the like.
Preferred xe2x80x9cspacer unitsxe2x80x9d S7 and S10 in the context of the present invention are a straight-chain or branched alkylene grouping, represented by xe2x80x94(CH2)rxe2x80x94, and also xe2x80x94Oxe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, wherein r and s are each an integer from 1 to 20, but especially from 2 to 12, with the proviso that r+sxe2x89xa621, especially xe2x89xa615, and wherein R2 represents hydrogen or lower alkyl.
Examples of preferred xe2x80x9cspacer unitsxe2x80x9d S7 and S10 are 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 3-methyl-1,4-butylene, 2-oxyethylene, 3-oxypropylene, 4-oxybutylene, 5-oxypentylene, 6-oxyhexylene, 7-oxyheptylene, 8-oxyoctylene, 9-oxynonylene, 10-oxydecylene, 11-oxyundecylene, 12-oxydodecylene, 2-(oxycarbonyl)ethylene, 3-(oxycarbonyl)propylene, 4-(oxycarbonyl)butylene, 5-(oxycarbonyl)pentylene, 6-(oxycarbonyl)hexylene, 7-(oxycarbonyl)heptylene, 8-(oxycarbonyl)octylene, 9-(oxycarbonyl)nonylene, 10-(oxycarbonyl)decylene, 11-(oxycarbonyl)undecylene, 12-(oxycarbonyl)dodecylene, 2-(carbonyloxy)ethylene, 3-(carbonyloxypropylene, 4-(carbonyloxy)butylene, 5-(carbonyloxy)pentylene, 6-(carbonyloxy)hexylene, 7-(carbonyloxy)heptylene, 8-(carbonyloxy)octylene, 9-(carbonyloxy)nonylene, 10-(carbonyloxy)decylene, 11-(carbonyloxy)undecylene, 12-(carbonyloxy)dodecylene, 2-(carbonylimino)ethylene, 3-(carbonylimino)propylene, 4-(carbonylimino)butylene, 5-(carbonylimino)pentylene, 6-(carbonylimino)hexylene, 7-(carbonylimino)heptylene, 8-(carbonylimino)octylene, 9-(carbonylimino)nonylene, 10-(carbonylimino)decylene, 11-(carbonylimino)undecylene, 12-(carbonylimino)dodecylene, 2-iminoethylene, 3-iminopropylene, 4-iminobutylene, 5-iminopentylene, 6-iminohexylene, 7-iminoheptylene, 8-iminooctylene, 9-iminononylene, 10-iminodecylene, 11-iminoundecylene, 12-iminododecylene, 2-iminocarbonylethylene, 3-iminocarbonylpropylene, 4-iminocarbonylbutylene, 5-iminocarbonylpentylene, 6-iminocarbonylhexylene, 7-iminocarbonylheptylene, 8-iminocarbonyloctylene, 9-iminocarbonylnonylene, 10-iminocarbonyldecylene, 11-iminocarbonylundecylene, 12-iminocarbonyldodecylene, 2-(2-ethyleneoxy)ethylene, 2-(3-propyleneoxy)ethylene, 6-(4-butyleneoxy)hexylene, 2-(2-ethyleneiminocarbonyl)ethylene, 2-(3-propyleneiminocarbonyl)ethylene, 6-(4-butyleneiminocarbonyl)hexylene, 6-(3-propyleneiminocarbonyloxy)hexylene, 6-(3-propyleneiminocarbonyl)hexylene and the like.
Preferred xe2x80x9cspacer unitsxe2x80x9d S8 and S9 in the context of the present invention are a straight-chain or branched alkylene grouping, represented by xe2x80x94(CH2)rxe2x80x94, and also xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94NR2xe2x80x94COxe2x80x94(CH2)rxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94NR2xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94COxe2x80x94NR2xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94COxe2x80x94NR2xe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94Oxe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94(CH2)rxe2x80x94NR2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94(CH2)rxe2x80x94Oxe2x80x94(CH2)sxe2x80x94Oxe2x80x94, wherein r and s are each an integer from 1 to 20, but especially from 2 to 12, with the proviso that r+sxe2x89xa621, especially xe2x89xa615, and wherein R2 represents hydrogen or lower alkyl.
Examples of preferred xe2x80x9cspacer unitsxe2x80x9d S8 and S9 are 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 3-methyl-1,4-butylene, 3-propyleneoxy, 3-propyleneoxycarbonyl, 2-ethylenecarbonyloxy, 4-butyleneoxy, 4-butyleneoxycarbonyl, 3-propylenecarbonyloxy, 5-pentyleneoxy, 5-pentyleneoxycarbonyl, 4-butylenecarbonyloxy, 6-hexyleneoxy, 6-hexyleneoxycarbonyl, 5-pentylenecarbonyloxy, 7-heptyleneoxy, 7-heptyleneoxycarbonyl, 6-hexylenecarbonyloxy, 8-octyleneoxy, 8-octyleneoxycarbonyl, 7-heptylenecarbonyloxy, 9-nonyleneoxy, 9-nonyleneoxycarbonyl, 8-octylenecarbonyloxy, 10-decyleneoxy, 10-decyleneoxycarbonyl, 9-nonylenecarbonyloxy, 11-undecyleneoxy, 11-undecyleneoxycarbonyl, 10-decylenecarbonyloxy, 12-dodecyleneoxy, 12-dodecyleneoxycarbonyl, 11-undecylenecarbonyloxy, 3-propyleneiminocarbonyl, 4-butyleneiminocarbonyl, 5-pentyleneiminocarbonyl, 6-hexyleneiminocarbonyl, 7-heptyleneiminocarbonyl, 8-octyleneiminocarbonyl, 9-nonyleneiminocarbonyl, 10-decyleneiminocarbonyl, 11-undecyleneiminocarbonyl, 12-dodecyleneiminocarbonyl, 2-ethylenecarbonylimino, 3-propylenecarbonylimino, 4-butylenecarbonylimino, 5-pentylenecarbonylimino, 6-hexylenecarbonylimino, 7-heptylenecarbonylimino, 8-octylenecarbonylimino, 9-nonylenecarbonylimino, 10-decylenecarbonylimino, 11-undecylenecarbonylimino, 6-(3-propyleneiminocarbonyloxy)hexylene, 6-(3-propyleneoxy)hexylene, 6-(3-propyleneoxy)hexyleneoxy, 6-(3-propyleneiminocarbonyloxy)hexyleneoxy, 6-(3-propyleneiminocarbonyl)hexyl, 6-(3-propyleneiminocarbonyl)hexyloxy, 1,2-ethylenedioxy, 1,3-propylenedioxy, 1,4-butylenedioxy, 1,5-pentylenedioxy, 1,6-hexylenedioxy, 1,7-heptylenedioxy, 1,8-octylenedioxy, 1,9-nonylenedioxy, 1,10-decylenedioxy, 1,11-undecylenedioxy, 1,12-dodecylenedioxy and the like.
The radicals K are divalent groups that can be derived from aliphatic, alicyclic or aromatic diamines by formal removal of the amino groups.
Preferred examples of such aliphatic and alicyclic diamines are:
ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, 1,7-heptylenediamine, 1,8-octylenediamine, 1,9-nonylenediamine, 1,10-decylenediamine, 1,11-undecylenediamine, 1,12-dodecylenediamine, xcex1,xcex1xe2x80x2-diamino-m-xylene, xcex1,xcex1xe2x80x2-diamino-p-xylene, (5-amino-2,2,4-trimethylcyclopentyl)methylamine, 1,2-diaminocyclohexane, 4,4xe2x80x2-diaminodicyclohexylmethane, 1,3-bis(methylamino)cyclohexane, and 4,9-dioxadodecane-1,12-diamine.
Preferred examples of aromatic diamines are:
3,5-diaminobenzoic acid methyl ester; 3,5-diaminobenzoic acid hexyl ester,
3,5-diaminobenzoic acid dodecyl ester; 3,5-diaminobenzoic acid isopropyl ester;
4,4xe2x80x2-methylenedianiline; 4,4xe2x80x2-ethylenedianiline; 4,4xe2x80x2-diamino-3,3xe2x80x2-dimethyldiphenylmethane; 3,3xe2x80x2,5,5xe2x80x2-tetramethylbenzidine; 4,4xe2x80x2-diaminodiphenyl sulfone; 4,4xe2x80x2-diaminodiphenyl ether; 1,5-diaminonaphthalene; 3,3xe2x80x2-dimethyl-4,4xe2x80x2-diaminobiphenyl;
3,4xe2x80x2-diaminodiphenyl ether; 3,3xe2x80x2-diaminobenzophenone; 4,4xe2x80x2-diaminobenzophenone;
4,4xe2x80x2-diamino-2,2xe2x80x2-dimethylbibenzyl; 2,2-bis[4-(4-aminophenoxy)phenyl]sulfone;
1,4-bis(4-aminophenoxy)benzene; 1,3-bis(4-aminophenoxy)benzene;
1,3-bis(3-aminophenoxy)benzene; 2,7-diaminofluorene; 9,9-bis(4-aminophenyl)fluorene; 4,4xe2x80x2-methylenebis(2-chloroaniline); 4,4-bis(4-aminophenoxy)biphenyl;
2,2xe2x80x2,5,5xe2x80x2-tetrachloro4,4xe2x80x2-diaminobiphenyl; 2,2xe2x80x2-dichloro4,4xe2x80x2-diamino-5,5xe2x80x2-dimethoxybiphenyl; 3,3xe2x80x2-dimethoxy-4,4xe2x80x2-diaminobiphenyl; 4,4xe2x80x2-(1,4-phenyleneisopropylidene)bisaniline; 4,4xe2x80x2-(1,3-phenyleneisopropylidene)bisaniline; 2,2-bis[4-(4-aminophenoxy)phenyl]propane; 2,2-bis[3-(4-aminophenoxy)phenyl]hexafluoropropane; 2,2-bis[3-amino-4-methylphenyl]hexafluoropropane; 2,2-bis(4-aminophenyl)hexafluoropropane; 2,2xe2x80x2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane;
4,4xe2x80x2-diamino-2,2xe2x80x2-bis(trifluoromethyl)biphenyl; and 4,4xe2x80x2-bis[(4-amino-2-trifluoromethyl)phenoxy]-2,3,5,6,2xe2x80x2,3xe2x80x2,5xe2x80x2,6xe2x80x2-octafluorobiphenyl.
The divalent, trivalent or tetravalent group J serves essentially as a grouping for linking the polymer main chain to the side-chain, which comprises the whole of formula I except M. Two of the valencies in J serve as linkages, indicated in formulae III to VIII, via S6 to S10 within the main chain. The third and optionally the fourth valency serves as the linkage to one or two side-chain(s) of the formula I (formula 1 except M). The polymer chain may, however, also comprise building blocks of the formulae II to VIII in which the side-chain of formula I is absent, that is to say where the group J is merely divalent. The proportion of building blocks of the formulae III to VII in which J is divalent, that is to say in which there is no crosslinkable side-chain of the formula I present, is generally less than 75%, but preferably less than 50% and more especially less than 30%. Of the trivalent and tetravalent groups J that contain one or two crosslinkable side-chains of the formula I, the trivalent groups, that is to say those groups which are linked to only one crosslinkable side-chain of the formula I, are preferred.
The photoactive polymer of formula I may be a bomopolymer or a copolymer. However, we prefer it to be a copolymer.
Preferably at least 50% of the monomer building blocks forming the main chain of photoactive polymer of formula I are linked to one or two side-chains, which U comprises the whole of formula I except M. Especially preferred is a polymer in which at least 70% of the monomer building blocks forming the main chain are linked to one or two of the side-chains.
Preferably the monomer building blocks carrying a side-chain are each linked to only one side-chain.
The building blocks of the formulae IV, VI and VIII are amic acid groupings or amic acid ester groupings (i.e. carboxamide-carboxylic acid groupings or carboxamide-carboxylic acid ester groupings) which on the one hand may occur as a result of incomplete imidisation in the polyimide chain. On the other hand, polymers that consist only of building blocks of formulae IV, VI or VIII, that is to say polyamic acids or polyamic acid esters, are important precursors for the preparation of the polyimides according to the invention and are also included in the present invention. Of those polymers which contain groups of formulae IV, VI or VIII, preference is given to those in which G is hydrogen, that is to say those which consist exclusively of, or contain some, polyamic acid groups.
The term xe2x80x9cphenylenexe2x80x9d includes in the context of the present invention 1,2-, 1,3- or 1,4-phenylene that is unsubstituted or mono- or poly-substituted. Preference is given to 1,3- or 1,4-phenylene, but especially to 1,4-phenylene.
The expression xe2x80x9ccyclic, straight-chain or branched alkyl residue which is unsubstituted or halogeno or polyhalogeno-substituted, having 1 to 12 carbon atoms and wherein one or more CH2 groups may independently be replaced by xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94CO, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, with the proviso that oxygen atoms are not directly attached to each otherxe2x80x9d denotes for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 3-methylpentyl, allyl, but-3-en-1-yl, pent4-en-1-yl, hex-5-en-1-yl, propynyl, butynyl, pentynyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, cyclopentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, 3-methylpentyloxy, allyloxy, but-3-enyloxy, pent-4-enyloxy, cylohexylmethoxy, cyclopentylmethoxy, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, 3-methylpentyloxycarbonyl, allyloxycarbonyl, but-3-enyloxycarbonyl, pent-4-enyloxycarbonyl, cylohexylnethoxycarbonyl, cyclopentylmethoxycarbonyl, acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, pentylcarbonyloxy, isopentylcarbonyloxy, cyclopentylcarbonyloxy, hexylcarbonyloxy, cyclohexylcarbonyloxy, octylcarbonyloxy, nonylcarbonyloxy, decylcarbonyloxy, undecylcarbonyloxy, dodecylcarbonyloxy, 3-methylpentylcarbonyloxy, but-3-enyloxy, pent-4-enyloxy, acetyl, ethylcarbonyl, propylcarbonyl, isopropylcarbonyl, butylcarbonyl, isobutylcarbonyl, sec-butylcarbonyl, pentylcarbonyl, isopentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, nonylcarbonyl, decylcarbonyl, undecylcarbonyl, dodecylcarbonyl, methoxyacetoxy, 1-methoxy-2-propoxy, 3-methoxy-1-propoxy, 2-methoxyethoxy, 2-isopropoxyethoxy, 1-ethoxy-3-pentyloxy, 3-butyn-1-oxy, 4-pentyn-1-oxy, 5-chloro-1-pentyn, 4-pentynecarbonyloxy, 6-propyloxyhexyl, 6-propyloxyhexyloxy, 2-fluoroethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 1H,1H-pentadecafluorooctyl, 1H,1H,7H-dodecafluoroheptyl, 2-(perfluorooctyl)ethyl, 2-(perfluorobutyl)ethyl, 2-(perfluorohexyl)ethyl, 2-(perfluorodecyl)ethyl, perfluoropropyl, perfluorobutyl, perfluoroheptyl, perfluorooctyl, perfluorononyl. 1-fluoropropoxy, 1-fluoropentyloxy, 2-fluoropropoxy, 2,2-difluoropropoxy, 3-fluoropropoxy, 3,3-difluoropropoxy, 3,3,3-trifluoropropoxy, trifluoromethoxy and the like.
The term xe2x80x9caliphaticxe2x80x9d, unless the context requires otherwise, includes straight-chain and branched alkyl, as well as saturated and unsaturated groups. Possible substituents include alkyl, aryl (thus giving an araliphatic group) and cycloalkyl, as well as amino, cyano, epoxy, halogen, hydroxy, nitro, oxo etc. Possible heteroatoms which may replace carbon atoms include nitrogen, oxygen and sulphur. In the case of nitrogen further substitution is possible with groups such as alkyl, aryl and cycloalkyl.
The term xe2x80x9calkylxe2x80x9d likewise, unless the context requires otherwise, includes straight-chain and branched alkyl, as well as saturated and unsaturated groups.
The term xe2x80x9clower alkylxe2x80x9d, denotes straight-chain and branched saturated hydrocarbon radicals having from 1 to 6, preferably from 1 to 3, carbon atoms, such as methyl ethyl, propyl or isopropyl and the like.
The term xe2x80x9caromaticxe2x80x9d includes carbocylic and heterocyclic groups, either unsubstituted or substituted by one or more groups.
The side-chain polymers according to the invention can be present in the form of homopolymers as well as in the form of copolymers. The term xe2x80x9ccopolymersxe2x80x9d is to be understood as meaning especially statistical copolymers.
The polymers of formula I are characterised by being readily accessible. The methods for the production will be known to a person skilled in the art.
The polymers of formula I, with acrylate, methacrylate and styrene derivative as repeating monomer unit, can be prepared in principle according to two different processes. In addition to the direct polymerisation of pre-finished monomers there exists the possibility of polymer-analogous reaction of reactive photoactive derivatives with functional polymers.
For the direct polymerisation, the monomers and the comonomers are firstly prepared separately from the individual components. The formation of the polymers is subsequently effected in a manner known per se under the influence of TV radiation or heat or by the action of radical or ionic catalysts. Potassium peroxodisulfate, dibenzoyl peroxide, azobisisobutyronitrile or di-tert-butyl peroxide are examples of radical initiators. Ionic catalysts are alkali-organic compounds such as phenyllithium or naphthylsodium or Lewis acids such as BF3, AlCl3, SnCl3 or TiCl4. The monomers can be polymerised in solution, suspension, emulsion or substance.
In the second process a polymer of formula I can also be produced in a polymer-analogous reaction from a pre-finished functional polymer and a suitable functionalised photoactive derivative. Many known processes such as, for example, esterification, trans-esterification, amidation or the etherification are suitable for polymer-analogous reactions.
This polymers have a molecular weight MW between 1000 and 5 000 000, preferably however between 5 000 and 2 000 000, especially advantageously however between 10 000 and 1 000 000.
The preparation of the polyamic acids and polyimides according to the invention is generally carried out analogously to the methods frequently described in the polyimide literature, for example Plast. Eng. 36 (1996) (Polyimides, fundamentals and applications).
For example, the polycondensation reaction for the preparation of the polyamic acids is carried out in solution in a polar aprotic organic solvent, such as xcex3-butyrolactone, N,N-dimethylacetamide, N-methylpyrrolidone or N,N-dimethylformamide. In most cases equimolar amounts of the dianhydride and the diamine are used, that is to say one amino group per anhydride group. If it is desired to stabilise the molecular weight of the polymer, it is possible for that purpose to add an excess or a less-than-stoichiometric amount of one of the two components or to add a monofunctional compound in the form of a dicarboxylic acid monoanbydride or in the form of a monoamine. Examples of such monofunctional compounds are maleic acid anhydride, phthalic acid anhydride, aniline and so on. The reaction is carried out preferably at a temperature of less than 100xc2x0 C.
The cyclisation of the polyamic acids to form the polyimides can be carried out by heating, that is to say by condensation with removal of water or by other imidisation reactions with reagents. When carried out purelythermally, the imidisation of the polyamic acids is not always complete, that is to say the resulting polyimides may still contain proportions of polyamic acid. The imidisation reactions are generally carried out at a temperature of from 60 to 250xc2x0 C., but preferably at less than 200xc2x0 C. In order to achieve imidisation at rather lower temperatures there are additionally mixed into the reaction mixture reagents that facilitate the removal of water. Such reagents are, for example, mixtures consisting of acid anhydrides, such as acetic acid anhydride, propionic acid anhydride, phthalic acid anhydride, trifluoroacetic acid anhydride, and tertiary amines, such as triethylamine, trimethylarmine, tributylamine, pyridine, N,N-dimethylaniline, lutidine, collidine etc. The amount of reagents used in that case is preferably at least two equivalents of amine and four equivalents of acid anhydride per equivalent of polyamic acid to be condensed.
The imidisation reaction can be carried out before or alternatively only after application to a support. The latter variant is preferred especially when the polyimide in question has poor solubility in the customary solvents.
The polyamic acids and the polyimides of the present invention has an intrinsic viscosity preferably in range of 0.05 to 10 dL/g, more preferably 0.05 to 5 dL/g. Herein, the intrinsic viscosity (xcex7inh=1n xcex7rel/C) is determined by measuring a solution containing a polymer in a concentration of 0.5 g/100 ml for its viscosity at 30xc2x0 C. using N-methyl-2-pyrrolidone as solvent.
The number of monomer building blocks from which the polymer chains according to the invention are synthesised can vary within a wide range. It is generally from 2 to 2000, but especially from 3 to 200.
The polymer according to the invention may contain additives such as silane-containing compounds and epoxy-containing crosslinking agents for further improving the adhesion of the polymer to a substrate. Example for silane adhesion promoters were described in the literature, for example Plast. Eng. 36 (1996) (Polyimides, fundamentals and applications). The above epoxy-containing crosslinking agent preferably includes 4,4xe2x80x2-methylenebis(N,N-diglycidylaniline), trimethylolpropane triglycidyl ether, benzene-1,2,4,5-tetracarboxylic acid 1,2:4,5-N,Nxe2x80x2-diglycidyldiimide, polyethylene glycol diglycidyl ether, N,N-diglycidylcyclohexylamine and the like.
The polymer according to the invention may contain additives such a photosensitiser, a photoradical generator and/or a cationic photoinitiator. Example for such additives were 2,2-dimethoxyphenylethanone, mixture of diphenylmethanone and N,N-dimethylbenzenamine or ethyl 4-(dimethylamino)benzoate, xanthone, thioxanthone, IRGACURE(trademark) 184, 369, 500, 651 and 907 (Ciba), Michler""s ketone, triaryl sulfonium salt and the like.
The polymers according to the invention may be used as a single polymer or as mixture with other polymers, oligomers, monomers, photoactive polymers, photoactive oligomers and/or photoactive monomers. Thus the properties of the layer may be modified to give what is sought. For example, an induced pretilt angles, good surface wetting, high voltage holding ratio, a specific anchoring energy etc. may be obtained.
The polymers according to the invention can then be applied to a support and, after any imidisation step which may be necessary, crosslinked by irradiation with linearly polarised light, that is to say by cycloaddition of their side-chains containing the photoreactive group, there being obtained, depending upon the direction of polarisation of the light radiated in, a preferred direction of orientation and of the angle of tilt for liquid crystals that are bought into contact with the orientation layer. By spatially selective irradiation of the molecular units according to the invention it is hence possible for very specific regions of a surface to be aligned and provided with a defined angle of tilt. At the same time the orientation layer so produced is also stabilised by the cycloaddition.
The present invention therefore relates also to the use of the polymers according to the invention as orientation layers for liquid crystals, and to their use in optical constictional elements, especially in the production of hybrid layer elements.
Such orientation layers can be produced, for example, by first preparing a solution of the resulting polymer material, which is applied to a support, which is optionally coated with an electrode (for example a glass plate coated with indium-tin oxide (ITO)), in a spin-coating apparatus, so that homogeneous layers of 0.05 to 50 xcexcm thickness are produced. Then, or optionally after prior imidisation, the regions to be oriented can be irradiated, for example, with a high-pressure mercury vapour lamp, a xenon lamp or a pulsed TV laser, using a polariser and optionally a mask for creating images of structures. The irradiation time is dependent upon the output of the individual lamps and can vary from a few seconds to several hours. The dimerisation can also be carried out, however, by irradiation of the homogeneous layer using filters that, for example, allow only the radiation suitable for the crosslinking reaction to pass through.
Further aspects of the present invention are:
a) Optical or electro-optical devices having at least one orientation layer, characterised in that the orientation layer contains polymers according to formula I; and
b) Use of polymer according formula I in the construction of unstructured and structured optical elements and multi-layer systems.